3.091 Introduction to Solid-State Chemistry - Fall 2013 Problem Set 13 Evaluation to be held on the final 1.

There are two stereo isomers of butene, cis 2-butene and trans-2-butene. Which molecule has a larger dipole moment? Which has higher boiling point?

2. Two specimens of polyethylene, one composed of linear chains and the other composed of branched chains, are solidified by identical cooling from the melt. The degree of polymerization is the same for both specimens. What is more likely to be suitable for use as a plastic food wrap?

3. Draw a trimer of isotactic polypropylene

4. Acrylonitrile, H2C=CH-CN, can be reacted by addition polymerization to form polyacrylonitrile (PAN). Draw a segment of syndiotactic PAN showing four repeat units.

5. 1-chlorobutene, ClHC=CH-CH2-CH3, can be reacted to form isotactic polychlorobutene (PCB) a. Does the reaction occur by addition or condensation? b. Draw a trimer of isotactic PCB c. What is the value of the degree of polymerization, n, of isotactic PCB with a molecular weight of 3 x 105 g/mole? d. Is isotactic PCB a thermoset or a thermoplastic? Explain e. Draw a schematic representation of the temperature dependence of the volume of linear isotactic PCB and branched PCB assuming both to be of comparable molecular weight. Label the T g of both substances.

6. Calculate the root mean squared length of a polypropylene molecule with molecular weight of 100,000 gm/mole.

7. A particularly strong rigid polyester used for electronic parts is marketed under the trade name Glyptal. It is a polymer of terephthalic acid and glycerol. Draw a segment of the polymer and explain why it is so strong.

8. Explain why a much stiffer foam is obtained if small amount of glycerol is added to the reaction mixture of toluene-2-6-diisocyanate and ethylene glycol during synthesis of a polyurethane foam.

9. Estimate the surface energy of the (100) face of Rh crystals given just the information in the periodic table.

10. Estimate the surface energy of the (110) face of K crystals given just the information in the periodic table.

11. How much larger will the surface energy be for a (100) face of Pt crystal if it is miss cut by 5 degrees?

12. What facets do you expect to appear on single crystals of Pt? What will be the equilibrium shape for these platinum crystals?

13. Two crystals of Pd are sitting next to one another. One has overall dimension of one micron the other has overall dimension of five microns. Which crystal has the larger energy per unit volume? How could the total energy be decreased?

14. The surface tension of an aqueous solution of a molecule is measured as a function of concentration. The data is shown below. Explain what is happening and why. How will the appearance of the solution differ at 0.001 wt% versus 1 wt.%?

15. Sketch how you expect the conductivity of an aqueous solution of SDS (CH3(CH2)11OSO3Na) to vary with concentration. Label all the relevant features of your sketch.

16. Sketch how you expect the surfactant surface concentration at the air water interface to change with aqueous solution concentration of the surfactant. Explain all relevant features of the sketch.

17. A surfactant known as Brij 30 has the structure C12H25(OCH2CH2)4OH. Sodium dodecyl sulfate (SDS) has the structure CH3(CH2)11OSO3Na. Which of these two surfactants has the lower CMC? Briefly explain your reasoning.

18. Why might SDS (CH3(CH2)11OSO3Na) form spherical micelles and phosphatidylcholine (shown below) form bilayer aggregates?